JPS62181115A - Manufacture of molded form prominent in optical characteristic - Google Patents

Abstract

PURPOSE:To obtain a molded form, prominent in transparency and small in optical distorsion by a method wherein carbonate resin, containing phosphite and specified in carbonate attaching unit as well as molecular weight, is employed. CONSTITUTION:Composition, in which 0.005-0.5wt% of phosphite is contained in polycarbonate resin consisting of polycarbonate attaching unit having a group whose unit attaching polycarbonate is shown by a formula (I) and/or (II) or (III) if necessary and show average molecular weight is 9,500-22,000, is injected and molded under a condition that resin temperature is 300-400 deg.C and mold temperature is 50-15 deg.C. In the formula (I), X, Y are the atom of hydrogen, the alkyl group of carbon number 1-6 and at least one of them is alkyl group or aralkyl group while, in the formula (II), A, B, Z, W are the atom of hydrogen or the alkyl group of carbon number 1-6 and at least one of A, B is the alkyl group having carbon number of 1-6.

Description

[Detailed description of the invention] [Field of application in sugar production] The present invention relates to a method for producing a molded product with excellent optical properties,
Specifically, the present invention relates to a method for producing a molded product with excellent transparency and low optical distortion.

[Conventional technology]

Resin moldings used for optical recording and reproducing purposes are required to be transparent and have small optical distortion. In particular, optical discs that are optical information recording materials that use digital signals, such as digital audio discs, digital video discs, and optical discs that are used for reading and writing information, have extremely strict requirements for transparency and optical distortion. The actual molded product is required to have birefringence of j×IO or less. Also,
This type of disk is also required to be free from scratches and to have excellent heat resistance.

In order to industrially produce such a molded article, it is advantageous to use a polycarbonate resin with excellent transparency, dimensional stability, heat resistance, etc., and to obtain the molded article by injection molding. In particular, in order to obtain a molded product with small optical distortion, a polycarbonate resin with a specific chemical structure is used, and during injection molding, the fluidity of the resin is improved to eliminate optical distortion caused by the flow of the molten resin. It is necessary to suppress uniform generation.

[Problem that the invention seeks to solve]

However, when the temperature of the molten resin is raised to improve the fluidity of the resin, various problems arise, such as yellowing and other discoloration due to the decomposition of the resin, which impairs the transparency of the resulting molded product. It hasn't arrived yet.

[Means for solving problems]

In view of the above points, the inventors of the present invention have repeatedly studied the loading of a method for producing a molded product with excellent transparency and low optical distortion. Polycarbonate resin with specific units and molecular weight has excellent melt flowability and stability against heat, and when injection molding is performed using this resin under specific conditions, molded products with good transparency and small optical distortion can be produced. We have discovered what can be done and arrived at the present invention.

[Structure of the invention]

The present invention provides a carbonate bond structural unit (component A) in which the unit constituting the carbonate bond has a group represented by the following general formula (1) and/or a carbonate bond structural unit having a group represented by the following general formula (II). (component B) and, if necessary, a carbonate-bonded structural unit (component C) having a group represented by the following general formula (III). θO~, 22,000 polycarbonate resin with 0.00 phosphite ester! ~θ, the composition containing 5% by weight was heated to a resin temperature of 300-%θ0°C,
Mold temperature 50~/! This is a method for producing molded products with excellent optical properties by injection molding at θ°C.

General formula (1) (wherein,
and at least seven of Y are aryl groups or aralkyl groups. ) General formula (II) (In the formula, A, B%2%W is a hydrogen atom or the number of carbon atoms/~
(B) is an alkyl group, and at least 7 of A and B are alkyl groups having a carbon number of /~ (B). ) General formula (1) is a valent group, where A and G are the amount of hydrogen or the number of carbon atoms/~
The alkyl group of (B) and D represent an alkylene group having a carbon number of 1 to 3. ) Hereinafter, the present invention will be explained in detail.

The carbonate bond in the present invention refers to a 10-C-0-bond obtained by reacting an alcoholic hydroxyl group or a phenolic hydroxyl group with, for example, phosgene, and the carbonate bond constituent unit refers to such a carbonate bond. refers to a divalent group interposed between two carbonate bonds.

The polycarbonate resin used in the present invention comprises a carbonate bonding structural unit (component A) having a group represented by the general formula (1) and/or a carbonate bonding structural unit (B) having a group represented by the general formula (II). component) and optionally a carbonate-bonded structural unit (component C) having a group represented by the above general formula (III).

A polycarbonate containing a carbonate bonding structural unit (component A) having a group represented by the general formula (1) can provide a group represented by the general formula (I). For example, it can be obtained by reacting and polymerizing one or more bisphenol compounds represented by the following general formula (I') with phosgene.

Examples of bisphenol-based compounds represented by the general formula (1') include bis(Hiroshi) -hydroxyphenyl)phenylmethane, /,
/-bis(Hiro-hydroxyphenyl)-/, -phenylethane, l,/-bis(Hiro-hydroxy:phenyl)-/-phenylpropa/, bis(Hiro-hydroxyphenyl) IJ/ phenylmethane, bis(4L -hydroxyphenyl) dibenzylmethane and the like. (Such a bisphenol compound is hereinafter referred to as bisphenol for component A.) A polycarbonate containing a polycarbonate bonding structural unit (component B) having a group represented by the above general formula (If) is a polycarbonate having a group represented by the above general formula (If). It can be obtained, for example, by reacting and polymerizing one or more bisphenol compounds represented by the following general formula (2) with phosgene.

General formula (■su (wherein, A, B%z, w are the general formula (I
It is synonymous with I). ) Examples of such bisphenol compounds represented by the general formula (II') include: bis(Hiro-hydroxy-3-methylphenyl)methane, /, l-bis(%-hydroxy-3-methylphenyl)
Ethane, tips. 2-bis(4t-hydroxy-3-methylphenyl)propane, co, corbis(Hiro-hydroxy-3-ethylphenyl)
Examples include propane, λ12-bis(%-hydroxy-J-isopropylphenyl)propane, 21.2-bis(me-hydroxy-J-sθC-butylphenyl)propane, and the like. (Such a bisphenol compound is hereinafter referred to as bisphenol for component B.) Furthermore, a carbonate-bonded structural unit (component C) having a group represented by the above general formula (III) is used as necessary in the present invention. The polycarbonate containing the above can provide a group represented by the general formula (1), for example, by reacting and polymerizing one or more of the bisphenol compounds represented by the following general formula (■) with phosgene. can.

General formula (■') (However, in the formula, E has the same meaning as the above general formula (III).) Examples of the bisphenol compound represented by the general formula (In') include his(9t-hydroxy phenyl)methane, /, /-bis(Hiro-hydroxyphenyl)ethane, /, /-bis(
Hiro - Hydroxyphenyl) Flopane, Tips. 2-bis(
9t-Hydroxyphenyl)propane or bisphenol A1 co, Corbis(nuhydroquiphenyl)butane, co,
Corbis(9L-hydroxyphenyl)pentane, λ,
2-upper 2-Hiro-hydroxyphenyl)-2-methylbutane, Co, Corbis (Hiro-hydroxyphenyl) hexane, Kotsu. Examples include 2-bis(9L-hydroxyphenyl>---methylpentane, /,/-bis(Hiro-hydroxyphenyl)cyclopentane, /,/-bis(5t-hydroxyphenyl)cyclohexa7, etc.). The bisphenol-based compound is hereinafter referred to as bisphenol for component C.) In the present invention, first, carbonate having a group represented by the general formula (1): a bonding structural unit (hereinafter referred to as component A) and/or a bisphenol compound having the general formula ( A carbonate bonding structural unit having a group represented by It) (hereinafter referred to as component B)
And if necessary, a polycarbonate resin having a carbonate bonding structural unit having a group represented by the general formula (III) (hereinafter referred to as component C) is prepared. The method includes a method in which bisphenol for component A or bisphenol for component B is reacted alone with phosgene and polymerized, and hisphenol for component A and bisphenol for Bg component are copolymerized, and if necessary, bisphenol for component C is copolymerized. and a method of copolymerizing bisphenol for component A or bisphenol for component B with bisphenol for component C.

Alternatively, bisphenol for component A, bisphenol for component B, and bisphenol for component C may be reacted with phosgene to obtain each polycarbonate, and then these minor polycarbonates may be mixed to meet the requirements of the present invention. good. Further, a copolymerized polycarbonate made from two or more of the bisphenols for components A, B, and C and a polycarbonate made from bisphenol containing the remaining components may be mixed so as to satisfy the requirements of the present invention.

For polymerization, the above-mentioned bisphenol compound and an aqueous alkaline solution or an acid acceptor such as pyridine are placed in an inert solvent containing methylene chloride and/or 2-dichloromethane, and phosgene is introduced into the mixture for reaction. . When using an alkaline aqueous solution as an acid acceptor, the reaction rate can be increased by using a tertiary amine such as trimethylamine or triethylamine or a tertiary ammonium compound such as tetrabutylammonium chloride or penzyltriptylammonium buhiromide as a catalyst. do. Further, if necessary, a monohydric 7-enol such as phenol or p-tert-butylphenol is allowed to coexist as a molecular weight regulator.

The reaction temperature is 0-700°C. The catalyst may be added from the beginning, or may be added in the middle of the reaction, that is, after the oligomer is produced, to carry out the polymerization reaction in the presence of the catalyst.

The method of copolymerizing the bisphenol for component A and/or B, and the bisphenol for component C used as necessary, is as follows: (a) They are present in the reaction system from the beginning and reacted with phosgene at the same time. Polymerize (b) After a portion of f and f are reacted with phosgene to some extent, the remaining component, bisphenol, is added and polymerized.

e→ Any method can be used, such as reacting with phosgene separately to form oligomers, then mixing them and further reacting to polymerize.

Furthermore, as a method of mixing separately polymerized materials,
After mixing each powder or granule, an extruder,
Any method can be used, such as a method of melting and mixing with a kneader 1 mixed wire roll or the like, a solution blending method, etc.

Component A and B of the polycarbonate resin used in the present invention
Content of component and C component ih, component A is 0 to 100% by weight in all carbonate bonding structural units, component B is ioo to O
Weight%, C component is 0 to 999471%, preferably 0 to 999471%
It is 0 weights t & chi.

Also, what is the average molecular weight of the polycarbonate resin used in the present invention? , J″00~koλ,000.

The average molecular weight referred to here is Bo') ma/s, Of/
l.

ηsp measured at 20°C using a methylene chloride solution of
It is a value obtained from the following formula (1) and formula (2).

ηap/c=(η)(/+to' ηsp) ・-
・・・・・・・・・(1) [η) = xu”
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・Song・(2) In the formula, C polymer concentration y
/t [η] Intrinsic viscosity, K'=0.2r +3 K/, 2ix10, a=Of! M
Average Molecular WeightIf the average molecular weight is too high, it is necessary to perform molding at a resin temperature of over 9LOO℃ in order to produce a molded product with little optical distortion, and decomposition of the resin can be avoided at such high temperatures. It is possible.

However, there are disadvantages such as silver streaks or coloring on the surface of the molded product. On the other hand, if the average molecular weight is too low, it is possible to obtain molded products with less optical distortion;
The resin has low strength and is easily damaged when the molded product is released from the mold, and even if a molded product is obtained, its mechanical strength is low.

Next, as the phosphorous acid ester used in the present invention, diesters or triesters of phosphorous acid and alcohols or phenols are preferably used, and among them, the following general formula (
Compounds represented by (2) are preferred.

General formula (■) (In the formula, R1 and R2 are an alkyl group having a carbon number of ~// or an aryl group having a carbon number of t to θ, R3 is a hydrogen atom, and an alkyl group having a carbon number of ~/r. Or carbon number 6-2
0 aryl group. ) R1 and R2 in general formula (IV) include butyl group, hexyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, octadecyl group,
Examples include alkyl groups such as a pentaerythrityl group and a cyclohexyl group, and an aryl group such as a phenyl group, a tolyl group, and a nonylphenyl group.

Furthermore, examples of R3 include a hydrogen atom, the above-mentioned alkyl group, or the above-mentioned aryl group.

Specific examples of such nitrous/acid esters include tributyl phosphite, tris(-monoethylhexyl) phosphite, tridecyl phosphite, tristearylphosphite, triphenyl phosphite, tricresyl phosphite, tris(nonylphenyl). ) phosphite, core ethylhexyl diphenyl phosphite, decyl diphenyl phosphite.

Phenyldi-ethylhexyl phosphite, pheterididecyl phosphite.

trichlohexyl phosphite.

Examples include distearylpene, taerythrityl phosphite, Schiffsenilpe/taerythrityl phosphite, and the like.

The content of soot/acid ester is polycarbonate xH! ¥1
relative to O6θθj~θ, 5% by weight, preferably latitude θ, θ
/~01.2% by weight. If the amount of phosphite ester is too small, it is impossible to suppress discoloration and deterioration of transparency due to decomposition of the resin.

On the other hand, if there is too much phosphite in Amashi, decomposition of the phosphite itself will be observed, causing problems such as silver streaks.

The method of incorporating phosphite into polycarbonate resin is the same as in the preparation method of ordinary resin compositions. Kneading method e→ Any method can be used, such as preparing master pellets with a high phosphite content and mixing them with polycarbonate resin.

Furthermore, in the present invention, when producing a molded product with excellent light-year characteristics by injection molding the above-mentioned polycarbonate resin introduction product, the resin temperature is set at 3θO to 00°C, and the mold temperature is set at so to /jSet as 0℃. If the resin temperature is set too high, the decomposition of the resin will be unavoidable, causing coloring, burst leaks, and poor transparency.

On the other hand, if the resin temperature is too low, a molded product with low optical distortion cannot be obtained even if the above-mentioned polycarbonate resin, which is less likely to cause optical distortion, is used.

one! In addition, the mold temperature is 50 to 750°C, preferably 60 to 750°C.
/91j℃. If the mold temperature is too high, deformation during mold release will increase, making it impossible to obtain a molded product with small bounce.

On the other hand, if it is too low, a molded product with small optical distortion cannot be obtained.

〔Example〕

Hereinafter, a specific method for producing the polycarbonate resin used in the present invention will be described as a production example, and a method for producing a disk using the obtained polycarbonate resin will be illustrated as an example.

Note that all "parts" indicating the components below are "parts by weight." The trace 1 constant value of hole ζ property is a value measured by the following method.

(stomach) ? 3. Center die of a disc with a thickness of 7.2 cm and a diameter of 30 mm, which was molded by JI. Evaluation was made using the phase difference (hereinafter abbreviated as Δn3,0., Δn3.5) due to birefringence at the OCm, S, and Sα positions. The phase difference due to refraction was measured using a polarizing microscope 1 manufactured by Nihon Kou Gakkogyo ■.

(B) Amount of Warpage Measured using a flatness tester FT-7 manufactured by K company.

(c) Is it better to use a flow tester with improved melt fluidity? θ℃, shear rate/θ
Differential melt viscosity η at "5ac-". was measured and used as a measure of melt fluidity.

The weight and average molecular weight of the polycarbonate resins produced in Production Examples/~3 and Comparative Production Examples/~λ are shown in Hikari-/ below. In addition, the results of Examples and Comparative Examples using these polycarbonate resins are shown in Tables 1 and 3 below.

Production example/ (a) Production of oligomer/, /-bis(Sc-hydroxyphenyl)-7-phenylethane 100 parts Ibin sodium hydroxide v0 part water
OO part methylene chloride
Charge 375 parts of the above mixture into a reactor equipped with a stirrer 1
It was stirred at 100 rpm. Phosgene was blown into this at a rate of 711/hour to effect interfacial polymerization.

After the reaction was completed, only the methylene chloride solution containing the polycarbonate oligomer was collected. The analysis results of the obtained oligomer solution in methylene chloride were as follows.

Oligomer concentration -2 parts! Weight% (Note/) Terminal chloroformate group concentration O6 standard (Note) Terminal phenolic hydroxyl group concentration 0.0λO standard (total 3) Note/) Measured by evaporation to dryness.

2) The aniline phosphate obtained by reacting with aniline is 0
．． Neutralization titration with 2N aqueous sodium hydroxide solution.

3) Titanium tetrachloride, colorimetrically measured at s 4t 4 nm when dissolved in acetic acid solution.

The oligomer solution obtained by the above method is hereinafter abbreviated as oligomer solution.

(b) Production of polycarbonate Oligomer solution - person / Hiro 0 parts p-tert-butylphenol 7.9 parts methylene chloride
? Part θ The above mixture was charged into a reactor equipped with a stirrer and stirred at jSOrpm. Furthermore, a water bath solution having the following composition, ie, 0 parts of a 7.3% by weight aqueous solution of sodium hydroxide and 7 parts of a 2% by weight aqueous solution of triethylamine, was added to carry out interfacial polymerization for 3 hours. The reaction mixture was separated and the methylene chloride solution containing the polycarbonate resin was mixed with water, aqueous hydrochloric acid solution,
The resin was then washed with water and finally the methylene chloride was evaporated to remove the resin. Average molecular weight of this resin
It was 20θ.

Production example λ (a) Production of oligomer 7 g of bisphenol A sodium salt prepared by dissolving bisphenol A in aqueous sodium hydroxide solution, 6 parts aqueous solution 100 parts p-tert-butylphenol 0.23 parts methylene chloride 1 part phosgene 2 A mixture having the above composition was constantly supplied to a pipe reactor to carry out interfacial polymerization.

The reaction mixture was separated and only the methylene chloride solution containing the polycarbonate oligomer was collected.

The analysis results of the obtained oligomer solution in methylene chloride were as follows.

Oligomer concentration: 2M, 5% by weight Terminal chloroformate group concentration: 7.3N Terminal phenolic hydroxyl group concentration: 0.3N or more The oligomer solution obtained by the method is hereinafter abbreviated as oligomer solution-B.

(b) Production of polycarbonate Oligomer solution-A, 20F oligomer solution-B j Hirobe Methylene chloride
/7 parts p-tertiary-butylphenol /9% 4 parts were charged into a reactor equipped with a stirrer. The mixture was stirred at θrpm. Furthermore, an aqueous solution having the following composition was charged and interfacial coalescence was performed for 2 hours.

water %
J' part Sodium hydroxide, 25 wt.% aqueous solution 39 parts Triethylamine 2 wt. It was f00.

In addition, from the NMR analysis results, the amount of copolymerized carbonate bond structural units derived from bisphenol A was 20.5% based on the total carbonate bond structural units. It was s weight.

Preparation Example 3 Oligomer Solution-B 37θ parts p-tert-butylphenol/, Om Methylene chloride 300 parts The above mixture was
Prepared in a reactor with PA,! ! The mixture was stirred at orpm. Furthermore, an aqueous solution having the following composition, that is, a 77% by weight aqueous solution of the sodium salt of co-1,2-bis(Hiro-hydroxy-3-methyl-7enyl)pupan.
2θθ part hydroxide) 2 parts of IJium #, % aqueous solution - 0 parts of triethylamine 2 parts
2 parts by weight aqueous solution was added, interfacial polymerization was carried out for about /, J'' hours, the reaction mixture was separated, and the methylene chloride solution containing the polycarbonate resin was washed with water, an aqueous hydrochloric acid solution, then water, and finally The methylene chloride was evaporated to give salt 9 of the resin.

The average molecular t of this resin is /7,000, NMF
From the analysis results of +, copolymerized co-, -bis(Hiroshi-
The amount of carbonate bonding units derived from hydroxy-3-methylphenyl)propane was 30.5% by weight based on the total carbonate bonding units.

Specific production example/In production example 3, p-tert-butylphenol 7
．． A polycarbonate resin was obtained by carrying out all the same operations except that 0 part was not used.

The average molecular weight of this resin is 23. Based on the NMR analysis results, the amount of copolymerized carbonate bond constituent units derived from co-corbis(Hiro-hydroxy-3-methylphenyl)propane is 3θ/wt% based on the total carbonate bond constituent units. Met.

Comparative production example 0 Agricultural production example of copolycarbonate resin / In (b), p
A polycarbonate resin was obtained by carrying out all the same operations except for changing the amount of -tertiary-butylphenol to 2.5 parts. Flat table of this resin -/, Composition and average molecular weight of the resin in Production Examples Examples/~3, Comparative Examples/~j Average molecules produced in Production Examples/! / /l-2θO polycarbonate resin flakes were mixed with the phosphite esters shown in Table-C below and the spears shown in Table-C to produce 9L01! !
The mixture was melt-kneaded and extruded into pellets using a IIIφ extruder at 210°C to obtain phosphite-containing polycarbonate resin pellets having the average molecular weight shown in Table 1.

This pellet is molded using an injection molding machine (M-7 Hiro 0A manufactured by Meikisha).
It was molded into a disk with a thickness of 7.2 cm and a diameter of 73 theta at the resin temperature and mold temperature shown in Table 2 using the following.

The phase difference and reciprocity due to birefringence of the obtained disk were as shown in Table 1. As shown in Table-2, Examples/
-3, it was possible to obtain a molded product with small optical distortion. On the other hand, silver streaks occurred when the resin did not contain phosphite as shown in Comparative Example 2 or when the resin temperature was too high as shown in Comparative Example 2. Further, when the resin temperature was too low as shown in Comparative Example 3, or when the mold temperature was too low as shown in Comparative Example 1, a molded product with small optical distortion could not be obtained. On the other hand, as shown in Comparative Example J, when the mold temperature was too high, the amount of cracking increased.

A disk was obtained by mixing a certain amount of tritethyl phosphite and carrying out the same operation as in Example.

The phase difference and amount of warpage due to birefringence of the obtained bata disk were as shown in Table 3.

As shown in Table 3, in Example 4t-6, a molded product with small optical distortion could be obtained. On the other hand, as shown in Comparative Example B, when the molecular weight of the resin was too high, a molded product with small optical distortion could not be obtained.

Furthermore, as shown in Comparative Example 2, if the molecular weight of the resin is too low, cracking occurs during molding, resulting in poor molding. [Effects of the Invention] As explained above, the method of the present invention improves transparency. It is possible to produce molded products with excellent yield, low birefringence, low warpage, and sufficient strength and heat resistance.

Representative of Mitsubishi Chemical Industries, Ltd.
Patent Attorney Hase - and 7 others

Claims (2)

[Claims] (1) The unit constituting the carbonate bond has the following general formula (
I) A carbonate-bonded structural unit having a group represented by (A component) and/or a carbonate-bonded structural unit (B component) having a group represented by the following general formula (II) and, if necessary, the following general formula (III) A composition in which a polycarbonate resin having an average molecular weight of 9,500 to 22,000 and containing 0.005 to 0.5% by weight of a phosphite ester is made of a carbonate bonding structural unit (component C) having a group represented by , resin temperature 300-400℃, mold temperature 5
A method for producing a molded product with excellent optical properties, characterized by injection molding at 0 to 150°C. General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula,
and at least one of Y is an aryl group or an aralkyl group. ) General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, A, B, Z, and W are hydrogen atoms or have 1 to 6 carbon atoms.
is an alkyl group, and at least one of A and B is an alkyl group having 1 to 6 carbon atoms. ) General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, E is a divalent group represented by ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, F and G represent hydrogen or an alkyl group having 1 to 6 carbon atoms, and D represents an alkylene group having 4 to 6 carbon atoms.) (2) Phosphite ester has the following general formula (IV) ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 and R^2 are alkyl groups with 4 to 18 carbon atoms or 6 to 20 carbon atoms and R^3 is a hydrogen atom, an alkyl group having 4 to 18 carbon atoms, or an aryl group having 6 to 20 carbon atoms. .